Method and apparatus for hydrogen production from water

ABSTRACT

A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH 4 . The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

This invention claims the benefit of priority from U.S. ProvisionalPatent Application Ser. No. 60/688,866 filed Jun. 8, 2005.

FIELD OF THE INVENTION

The present invention provides a new method and chemical compositionsfor producing hydrogen from water and methods and apparatuses for usingthese compositions in energy-related applications, e.g., powergeneration using fuel cells, heating, etc.

BACKGROUND AND PRIOR ART

Hydrogen is universally considered a fuel of the future due toenvironmental advantages over conventional (i.e., fossil-based) fuels.Another important advantage of using hydrogen stems from the fact thatit could be electrochemically (i.e., without Carnot-cycle limitation)converted into electricity with very high energy conversion efficiencyusing fuel cells (FC).

To be used in energy conversion devices, hydrogen has to be produced andstored; however, each of these aspects of hydrogen technology isassociated with major technological challenges. Conventional(non-electrolytic) hydrogen production processes (for example, steammethane reforming) are complex, multi-stage devices that producesignificant amounts of carbon dioxide (CO₂) emissions at the productionsite and, besides, are very difficult to down-scale (e.g., tosub-kilowatt range). Hydrogen storage is another major roadblock to awidespread use of hydrogen in power generation systems. Conventionalhydrogen storage systems in the form of a compressed gas, or a liquid,or a metal hydride, suffer from either low gravimetric and volumetricdensities, or high cost, or safety-related problems, and the like.

Various methods for generating or producing hydrogen based on thereactions of metal hydrides or metals or their alloys with water areknown and are referenced below.

S. Amendola et al. in U.S. Pat. No. 6,534,033 B1 describes a system forhydrogen generation, and in U.S. Pat. No. 6,683,025 B2 describes aprocess for making hydrogen generation catalysts. Both patents involve amethod for storage and controlled release of hydrogen via use of sodiumborohydride-based solutions and a catalytic system.

Patent Cooperation Treaty (PCT) publication, WO 2004/035,464 to R. Chendescribes hydrogen generation apparatus in which a hydride (stabilizedNaBH₄) is decomposed by a catalyst to produce hydrogen and wasteproducts.

Methods for producing hydrogen using aluminum and water are disclosed inU.S. Pat. No. 6,506,360 B1 to Andersen et al., PCT publication WO2002/08118 01 to Andersen et al. entitled, “Hydrogen production fromaluminum, water and sodium hydroxide,” US Patent Appl. Publ.2003/0143155 to Andersen et al.; PCT publication WO 2004/052775 toAndersen et al. entitled, “Method for producing hydrogen from aluminum”,U.S. Patent Appl. Publ. 2004/0115125 to E. R. Andersen et al. entitled,“Renewable energy carrier system and method.” A method and an apparatusfor producing hydrogen include reacting aluminum with water in thepresence of NaOH as a catalyst. The reaction vessel contains 0.26-19 Maqueous solution of NaOH.

PCT publication WO 02/06153 A1 to E. Baldwin et al. discloses a methodof contacting an aqueous liquid (alkali metal hydroxide) with adissociation initiating material (Al or Na—Al alloys) in a reactionvessel and controlling the surface area of dissociation and pressuretherein.

PCT publication WO 2002/14213 A2, to A. Chaklader, et al. discloses amethod for producing hydrogen by reacting a metal selected from Al, Mg,Si, Zn with water in the presence of a catalyst at pH between 4 and 10.

U.S. Patent Application Publ. US 2004/0018145 A1, to T. Suzuki et al.discloses a method wherein water and MgH₂ react to produce targethigh-pressure hydrogen in a high-pressure container.

A Japanese patent JP 62263946 to H. Kudo et al. describes the use ofquenched aluminum-bismuth alloy for hydrogen production wherein Al—Bialloy (solidified at >104° C./s) produced hydrogen by dipping in 70° C.water.

A Soviet Union patent, SU 945061 (1982) to L. Kozin et al. disclosed analuminum-based composition for preparing hydrogen; Al—Hg (3-5 wt. %)alloy was used to produce hydrogen from water.

K. Scherbina in “Solid-phase reaction products in hydrogen generationprocesses,” Problemy Mashinostroeniya (1983), v. 20, pp. 83-86 (inRussian) reports that hydrogen was produced by decomposition of waterwith Al—Li (16%), Al—Li(50%), Al—Na(50%) composites.

Another Soviet Union patent, SU1675199 (1991) to M. Khazin et al.describes the use of aluminum-iron-silicon alloy for producing hydrogenby decomposition of water. The alloy for the efficient production ofhydrogen contains Ca (0.1-1%), Na (0.01-1%), Cu (0.1-3%), Fe(5-15%), thebalance-Si.

Additional methods for producing hydrogen and heat energy are disclosedby A. Yelkin et al. in PCT publications WO 2003/104344 and WO 2002/14214A1. The methods consist of preparing a composition based on activatedtextured aluminum or Al-containing material and reacting it with water.The activation of Al is carried out by means of applying molten fusiblemetals with low melting point (Ga, Sn, In) to the end surface of Al.

G. Antonini et al. in “Hydrogen generation from concentratedaluminum-water suspensions. Application for continuous heat productionby catalytic combustion.” Recents Progres en Genie des Procedes (1991) 5(16) pp. 81-86. A process was developed for chemical storage of hydrogenas concentrated suspensions of Al powder in H2O/NaOH. The suspension canbe made to produce hydrogen on demand. Hot water for the reaction istaken from a boiler where catalytic combustion of hydrogen is carriedout.

M. Matsuyama et al. in “Hydrogen production from water using wastealuminum.” Toyama Daigaku Suiso Doitai Kino Kenkyu Senta Hokoku (1992)12, pp. 49-58 discusses factors affecting the rate of hydrogenproduction from water using Al and Al—Mg alloys were investigated.

In British patent GB 2344110 to G. Carloss, the production of alloygranules for hydrogen generation is discussed. The granules are madefrom Al, Sn, Zn and trace amounts of Si and Sb. The granules react withhot water with the production of hydrogen gas.

Hydrogen generation is observed in the wet cutting of Al and its alloysdue to the reaction between the fresh surface of Al with water asreported by K. Uehara et al. in “Hydrogen gas generation in the wetcutting of aluminum and its alloys” J. Mater. Proc. Techn. (2002) 127,pp. 174-177.

Aluminum samples in the form of a cylindrical block, powder or pelletsreact with aqueous solutions of NaOH to generate hydrogen gas arediscussed by D. Belitskus, in “Reaction of aluminum with sodiumhydroxide solution as a source of hydrogen,” J. Electrochem. Soc. (1970)117, pp. 1097-1099.

It should be noted, however, that the systems based on metal hydrides,and particularly complex metal hydrides, are rather costly and requirepreliminary preparation of reacting solutions and the use of expensivenoble metal based catalysts. Metal-based systems also suffer from anumber of shortcomings. Metals or alloys, such as, Li, Na, K, Ca, Al—Hg,Al—Li, Al—Na, Si—Al—Ca—Na—Fe—Cu, that directly react with water atambient temperature are either expensive, or hazardous, or present greatsafety concerns, including, violent uncontrolled reaction with water. Onthe other hand, such inexpensive and readily available materials likealuminum (Al) and its alloys and iron (Fe) and its alloys do not reactwith water at ambient temperature. Al can release hydrogen from aqueoussolutions only in the presence of substances, such as, alkalihydroxides: NaOH, KOH, that remove a protective oxide layer from Alsurface and, as a result, are consumed in the process, since they aretransformed into respective aluminates.

Thus, there is a need for an efficient, simple and inexpensivehydrogen-generating system and a device that could be easily adopted todifferent capacities from watts to kilowatt range. There is also a needfor a method and an apparatus to safely produce hydrogen using water andother readily available materials in locations where it may beconveniently used for heat and/or electricity generation. There is alsoa need for more efficient chemical compositions that exceed theperformance characteristics, such as, specific energy, power density, ofthe state-of-the-art hydrogen-generating systems.

The present invention improves upon the deficiencies of the prior artwhich include, but are not limited to, the following.

The disclosed system has greater power density (i.e., amount of hydrogenproduced from unit of weight or volume of the reagents used) compared toprior art. The present invention is simpler and more compact. Hydrogenis produced directly from water, not from reacting solutions ofwater-soluble hydrides as in prior art. Hydrogen production startsimmediately upon the addition of water without any induction orwarming-up period. The present invention utilizes inexpensive readilyavailable reagents and catalysts.

SUMMARY OF THE INVENTION

A primary objective of the present invention is to provide a method forproducing hydrogen from water and hydrogen-containing compounds.

A secondary objective of the present invention is to provide anapparatus for producing hydrogen from water and hydrogen-containingcompounds.

A third objective of the present invention is to provide chemicalcompositions for producing hydrogen from water and hydrogen-containingcompounds.

A fourth objective of the present invention is to provide chemicalcompositions capable of reacting with water to produce hydrogen atambient conditions of temperature and pressure.

A fifth objective of the present invention is to provide compounds thatcatalyze the release of hydrogen from water and hydrogen-containingcompounds at ambient conditions of temperature and pressure.

A sixth objective of the present invention is to provide chemicalcompositions for producing hydrogen from water and hydrogen-containingcompounds that are easily disposed of and/or regenerated into originalreagents.

A seventh objective of the present invention is to provide a method,apparatus and chemical composition that produces high purity hydrogengas (>99.9 volume %).

A preferred method for producing hydrogen from water includes selectingat least one metallic ingredient that can release hydrogen when reactingwith water, selecting at least one inorganic hydride that can releasehydrogen when reacting with water, selecting at least one transitionmetal compound that can catalyze the reaction of metallic ingredient andinorganic hydride with water, keeping the metallic ingredient andinorganic hydride separate until the reaction with water is desired forthe production of hydrogen, placing the metallic ingredient in a firstholding area and the inorganic hydride in a second holding area within avessel without water, adding water to the vessel to cover the holdingarea with the metallic ingredient and the holding area with theinorganic hydride, and collecting hydrogen released from thedecomposition of water in a synergistic reaction of metallic ingredientand inorganic hydride.

The metallic ingredient in the preferred method is selected fromelements of groups IIA-IVA and VIII and alloys thereof and preferablyinclude aluminum (Al), magnesium (Mg), silicon (Si), iron, aluminumalloys, magnesium alloys, iron alloys and silicon alloys; mostpreferably, the metallic ingredient is aluminum.

The preferred inorganic hydride is selected from a family of inorganiccomplex metal hydrides and includes sodium borohydride, lithiumborohydride, potassium borohydride, lithium aluminum hydride, sodiumaluminum hydride; most preferably, the inorganic hydride is sodiumborohydride.

It is also preferred to add an alkali metal-based compound to theinorganic hydride prior to adding water to the vessel and add atransition metal compound from groups VIII and IB to the metallicingredient prior to adding water to the vessel to catalyze the aqueousreaction resulting in hydrogen release.

The preferred alkali metal-based compound that is added to the inorganichydride is at least one of sodium hydroxide (NaOH), potassium hydroxide(KOH), lithium hydroxide (LiOH), sodium carbonate (Na₂CO₃), andpotassium carbonate (K₂CO₃); most preferably the alkali metal-basedcompound is sodium hydroxide (NaOH).

The preferred transition metal and its compound is cobalt, cobaltchloride (CoCl₂), cobalt bromide (CoBr₂), cobalt iodide (CoI₂), cobaltnitrate (Co(NO₃)₂, iron, iron (II) chloride (FeCl₂), iron (III) chloride(FeCl₃), ruthenium, ruthenium (III) chloride (RuCl₃), copper, coppersulfate (CuSO₄), platinum, chloroplatinic acid (H₂PtCl₆), nickel, nickelnitrate (Ni(NO₃)₂ and nickel chloride (NiCl₂); most preferably thetransition metal compounds are cobalt chloride (CoCl₂) and iron chloride(FeCl₂).

A preferred composition capable of decomposing water and releasinghydrogen without the need for additional reagents or elevatedtemperatures contains a separate amount of a metallic ingredient thatcan release hydrogen when reacting with water in a reaction vessel, aseparate amount of an inorganic hydride that can release hydrogen whenreacting with water in a reaction vessel, and a separate amount of atransition metal compound that can catalyze the reaction of the metallicingredient and inorganic hydride with water.

The preferred metallic ingredient in the composition of the presentinvention is selected from elements of groups IIA-IVA and VIII andalloys thereof, preferably aluminum (Al), magnesium (Mg), silicon (Si),iron (Fe), aluminum alloys, magnesium alloys, iron alloys and siliconalloys; most preferably, the metallic ingredient is aluminum.

The preferred inorganic hydride of the composition of the presentinvention is selected from a family of complex inorganic hydrides whichincludes, but is not limited to, sodium borohydride, lithiumborohydride, potassium borohydride, lithium aluminum hydride, sodiumaluminum hydride; most preferably, the inorganic hydride is sodiumborohydride.

The preferred composition of the present invention also includes analkali metal-based compound added to the inorganic hydride prior tocontact with water in a reaction vessel, and a transition metal compoundfrom groups VIII and IB added to the metallic ingredient prior tocontact with water in a reaction vessel to catalyze the aqueous reactionresulting in hydrogen release.

The preferred alkali metal-based compound is at least one of sodiumhydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH),sodium carbonate (Na₂CO₃), and potassium carbonate (K₂CO₃); mostpreferably, the alkali metal-based compound is sodium hydroxide (NaOH).

The preferred transition metal and its compound is cobalt, cobaltchloride (CoCl₂), cobalt bromide (CoBr₂), cobalt iodide (CoI₂), cobaltnitrate (Co(NO₃)₂, iron, iron (II) chloride (FeCl₂), iron (III) chloride(FeCl₃), ruthenium, ruthenium (III) chloride (RuCl₃), copper, coppersulfate (CuSO₄), platinum, chloroplatinic acid (H₂PtCl₆), nickel, nickelnitrate (Ni(NO₃)₂ and nickel chloride (NiCl₂); most preferably, thetransition metal compound is cobalt chloride (CoCl₂) and iron chloride(FeCl₂).

A preferred apparatus for producing high purity hydrogen from thedecomposition of water, is a reaction vessel having a lower part and anupper part, a bellows-shape wall portion forming the upper part of thevessel, a first holding area for a metallic component in the upper partof the vessel, a second holding area for an inorganic hydride in thelower part of the vessel, a rod to support the holding area for themetallic component extending through the upper bellows-shape wallportion to the lower part of the vessel, an inlet for water with a capintegrally attached and protruding upward from the bellows-shape portionof the vessel, an outlet for hydrogen with a valve extending upward fromthe bellows-shape portion of the vessel, an outlet for a spent solutionof reagents used in the reaction to release hydrogen extending downwardfrom the lower part of the reaction vessel, and water to cover theholding area for an inorganic hydride and the holding area for themetallic component that is supported by a rod.

The preferred metallic ingredient is selected from elements of groupsIIA-IVA and VIII and alloys thereof which include, but are not limitedto, aluminum (Al), magnesium (Mg), silicon (Si), iron (Fe), aluminumalloys, magnesium alloys, iron alloys and silicon alloys; mostpreferably, the metallic ingredient is aluminum.

The preferred inorganic hydride is selected from a family of complexinorganic hydrides, including, but not limited to, sodium borohydride,lithium borohydride, potassium borohydride, lithium aluminum hydride,sodium aluminum hydride; most preferably the inorganic hydride is sodiumborohydride.

Another preferred apparatus for producing high purity hydrogen from thedecomposition of water includes a reaction vessel having a first chamberfor receiving a plurality of reactant capsules prior to the addition ofwater to the vessel and a second chamber to accommodate the aqueousreaction water from the first chamber when the reaction is stopped, apiston and tension spring assembly connected to the second chamber toaccommodate pressure that builds when the reaction is stopped, asupporting grid to support the plurality of reactant capsules, an inletfor water with a cap integrally attached and protruding upward from thefirst chamber of the vessel, an outlet for hydrogen with a valve to stopthe flow of hydrogen and move the aqueous reaction water to the secondchamber, said valve extending upward from the top portion of the vessel,and an outlet for a spent solution of reagents used in the reaction torelease hydrogen extending downward from the bottom of the first chamberof the reaction vessel.

One of the plurality of reactant capsules preferably contains an alkalimetal-based compound that is at least one of sodium hydroxide (NaOH),potassium hydroxide (KOH), lithium hydroxide (LiOH), sodium carbonate(Na₂CO₃), and potassium carbonate (K₂CO₃); most preferably, the alkalimetal-based compound is sodium hydroxide (NaOH).

Another of the plurality of reactant capsules preferably contains atransition metal and its compound that is at least one of cobalt, cobaltchloride (CoCl₂), cobalt bromide (CoBr₂), cobalt iodide (CoI₂), cobaltnitrate (Co(NO₃)₂, iron, iron (II) chloride (FeCl₂), iron (III) chloride(FeCl₃), ruthenium, ruthenium (III) chloride (RuCl₃), copper, coppersulfate (CuSO₄), platinum, chloroplatinic acid (H₂PtCl₆), nickel, nickelnitrate (Ni(NO₃)₂ and nickel chloride (NiCl₂); most preferably, thetransition metal compound is cobalt chloride (CoCl₂) and iron chloride(FeCl₂).

The water used for the reaction to release hydrogen includes, but is notlimited to, tap water, reclaimed water, industrial grade water, and seawater.

Further objects and advantages of the present invention will be apparentfrom the following detailed description of a presently preferredembodiment which is illustrated schematically in the accompanyingdrawings.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 provides a clear illustration of the synergistic action of thecomponents of the composition during the release of hydrogen from water.

FIG. 2 is an illustration of one preferred embodiment of the apparatusfor hydrogen production according to the present invention.

FIG. 3 is an illustration of the second preferred embodiment of theapparatus for hydrogen production according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Before explaining the disclosed embodiments of the present invention indetail it is to be understood that the invention is not limited in itsapplication to the details of the particular arrangements shown sincethe invention is capable of other embodiments. Also, the terminologyused herein is for the purpose of description and not of limitation.

The present invention provides a novel method, apparatuses and chemicalcompositions for producing hydrogen from water and hydrogen-containingcompounds. The new chemical compositions include at least twocomponents: A and B, and, preferably, a third component C, and,optionally, a fourth component D. The component A includes at least onemetal or alloy. Although the reaction of the component A with water whenproducing hydrogen is thermodynamically favorable, it does not occur atambient conditions of temperature and pressure or slightly elevatedtemperatures (up to 100° C.) due to a protective oxide layer on themetal or alloy surface. The component B includes one or more inorganicmetal hydrides that can release hydrogen in aqueous solutions at ambientconditions in the presence of catalytic materials or without catalyticmaterials. The composition also includes one or more transition metalsor their compounds (the component C) that can catalyze the release ofhydrogen and, optionally, one or more alkali metal-based compounds (thecomponent D) to stabilize the component B and accelerate the reaction ofthe component A with water.

The component A of the composition is selected from the elements ofgroups IIA-IVA and VIII (e.g., Al, Mg, Si, Fe, etc.), preferably, Al andits common alloys. The component B is selected from a family ofinorganic metal hydrides including, but not limited to, NaBH₄, LiBH₄,KBH₄, LiAlH₄, NaAlH₄, AlH₃, preferably, NaBH₄. The present inventioncomposition also includes the component C, which is selected from thetransition metals and their compounds from the groups VIII and IBincluding, but not limited to, Co, CoCl₂, CoBr₂, CoJ₂, Co(NO₃)₂, Ni,Ni(NO₃)₂, NiCl₂, Ru, RuCl₃, Fe, FeCl₂, FeCl₃, Pt, H₂PtCl₆, Cu, CuSO₄,preferably, CoCl₂, FeCl₂. These compounds may be used in the form offine powders, thin films deposited on the surface of the component A, orsupported on a solid substrate such as Al₂O₃, SiO₂, activated carbon,molecular sieves, etc, preferably, Al₂O₃. The disclosed compositionoptionally includes the component D, which is selected from alkalimetal-based compounds, such as, NaOH, KOH, LiOH, Na₂CO₃, K₂CO₃,preferably, NaOH.

The hydrogen production method disclosed in the present inventioninvolves adding water to a chemical composition consisting of thecomponents A, B (stored separately before the reaction) and C and,optionally, D mixed at certain ratios at the moment when the release ofhydrogen gas is desirable. It should be emphasized that neithercomponent of the composition (except, the component B) is able to reactwith water to produce hydrogen at room temperature. In some cases, e.g.,NaBH₄, the component B very slowly reacts with water at ambienttemperature. The component C can catalyze the reaction of bothcomponents A and B with water. The function of the component D is tostabilize the component B before the reaction (i.e., to prevent slowspontaneous decomposition of B) and also to facilitate the reaction ofthe component A with water.

The novelty of the invention resides in the synergistic action of thecomponents A and B that lead to a facilitated reaction of bothcomponents with water and the release of hydrogen therefrom. Althoughthermodynamically favorable, the reaction of Al (component A) with waterdoes not occur at room or elevated (up to 100° C.) temperatures withoutthe presence of a special reagent that eliminates the protective oxidelayer from its surface. On the other hand, some complex metal hydridessuch as sodium borohydride (component B) very slowly react with water atambient conditions and usually require a catalyst to facilitate thereaction. When mixed together, the components A and B form a novelchemical composition that is able to decompose water and releasehydrogen without the need for additional reagents. This becomes possibledue to the catalytic action of the component A on the reaction of B withwater; at the same time, the component B activates the component A(i.e., Al) by removing oxide layer from its surface and, thus,facilitates its reaction with water. In generalized form, the mainreaction can be represented in the form of the following equation:A+B+nH₂O→nH₂+(AB)O_(n)  (1)where, (AB)O_(n) denotes the final product of the transformation of thecomponents A and B in an aqueous solution.

The addition of the component C to the composition accelerates thereactions of both components A and B with water, and, thus facilitatesthe overall process. It should be noted that the component C is alsocapable of accelerating the reactions of the components A and B withwater separately (i.e., without the presence of a third component, suchas B and A, respectively). In a generalized form:A+H₂O+(C)→H₂+AO+(C)  (2)B+H₂O+(C)→H₂+BO+(C)  (3)where, C is the component C of the chemical composition, and AO and BOdenote the final products of the transformation of the components A andB, respectively, in the presence of C in aqueous solutions.

The function of the component D is to stabilize the component B (i.e.,to prevent its premature moisture-induced decomposition). Anotherimportant role of the component D is to accelerate the reaction of thecomponent A with water by removing the protective oxide layer from itssurface. In a general form:A+H₂O+(D)→H₂+(AD)O  (4)where, D is the component D of the chemical composition, and (AD)Odenotes the final product of the transformation of the components A andD in an aqueous solution.

Table 1 below provides a generic composition of the present invention.

TABLE 1 Composition for Hydrogen Production from Water Illustrativeexample of Concentration Component the component range, wt. % A Aluminum(Al) 10-80 B Sodium borohydride (NaBH₄) 15-75 C Cobalt chloride (CoCl₂)0.1-20  D Sodium hydroxide (NaOH) 0.5-50 

Example 1

In a three-part experiment illustrated in FIG. 1, first, 0.27 g of Alfoil (the component A) was brought into contact with 100 ml of water: nohydrogen production was observed at 50° C. (curve 1 on FIG. 1). In thesecond part, 0.38 g NaBH₄ (the component B) was stabilized with 0.47 gof NaOH (the component D) and the mixture was added to 100 ml of waterat 50° C., which resulted in some slow release of hydrogen gas (curve2). (It should be noted that adding more NaOH to NaBH₄ results in morestabilization of the latter and, hence, even slower release ofhydrogen). In the third part of the experiment, 0.27 g of Al foil and(0.38 g) of NaBH₄ were brought into contact with water and each other ina vessel (at 50° C.). This resulted in a fast (but controlled) reactionbetween the components of the mixture and water and led to the energeticrelease of hydrogen gas from water and the hydride (curve 3). There wasunreacted Al foil (0.149 g) remaining in the vessel after 1 hour. Thevolume of hydrogen produced after one hour was 1,205 ml, which isroughly equal to the sum of stoichiometric volumes of hydrogen thatwould be generated from Al and NaBH₄ if they reacted with waterseparately (1,141 ml). The purity of hydrogen gas produced exceeded99.99 vol. % (on dry basis). Hydrogen gas did not contain any harmfulcontaminants such as carbon monoxide, hydrogen sulfide, ammonia, etc.,therefore it was directly fed to polymer electrolyte membrane (PEM) fuelcell to produce electricity.

Example 2

0.27 g of Al powder (component A) was mixed with 0.02 g of CoCl₂(component C) and ground in an agate mortar to form a uniform finepowder. Separately, 0.39 g of NaBH₄ (component B) was mixed with 0.22 gof NaOH (component D). The second mixture was added to 100 ml ofdistilled water at room temperature, followed by adding the firstmixture to the resulting solution. An immediate release of hydrogen gaswas observed. The amount of hydrogen gas produced was 1.40 liters, whichcompares favorably within the experimental margin of error (5%) with thestoichiometric amount of hydrogen (1.34 liters).

Referring now to FIG. 2, there is an illustration of the apparatus thatis preferred for the present invention. However, a judicious selectionof apparatus is required by someone skilled in the art and is not alimitation of the present invention. The apparatus 20 consists of twosections: bottom cylindrical part 21 and upper bellow-shaped part 22.The component A or the mixture of A and C is placed in a holder 23 thatis attached to the upper section of the vessel by a rod 26. Thecomponent B or the mixture of B and D is placed in a holder 25 that isattached to the bottom section of the vessel. When hydrogen is needed,water is introduced into the vessel 20 through the inlet 27. Waterdissolves the component B (or B plus D) in holder 25, and the resultingsolution reacts with the component A (or A plus C) in holder 23 with therelease of hydrogen gas from water and the component B. Hydrogen gasexits the vessel through an outlet 28 having a valve 29. When hydrogenis no longer needed, the valve 29 is closed, causing pressure in thevessel to increase and expand the bellow-shape section the vessel 22upward. The holder 23 with the component A is drawn out of the reactingsolution 24 and the hydrogen generation reaction stops. Hydrogenpressure in the exit line is regulated by the tension of a plurality ofsprings 30. The waste solution, after depletion of the components A andB, is withdrawn from the vessel through an outlet 31. Since the purityof hydrogen gas produced exceeds 99.99 vol. % (on dry basis), and itdoes not contain any potentially harmful contaminants such as carbonmonoxide, hydrogen sulfide, ammonia, and the like; hydrogen can bedirectly fed to any type of fuel cell, including PEM fuel cell, toproduce electricity.

FIG. 3 depicts another preferred embodiment of the inventive apparatus.The apparatus 40 consists of two chambers 41 and 42 divided by apartition 43. The components A (or A plus C) and B (or B plus D) areplaced in two separate capsules 44 and 45, respectively. Reactantcapsules 44 and 45 each have water-dissolving polymeric jackets. Bothcapsules are dropped on a grid 46 through a lid 47. When hydrogen isneeded, water is introduced into the vessel 40 through an inlet 48causing the reaction between the components of the composition to startand release hydrogen gas that exits through an outlet 49. By closing thevalve 50, the operator stops the flow of hydrogen and simultaneouslypushes the reacting solution 51 from the chamber 41 into the chamber 42,and the reaction ceases. The pressure of hydrogen in the exit line iscontrolled by the tension of a spring 52 in a piston 53 connected to thechamber 42 through a tubing 54. A waste solution can be dislodged froman outlet 55. FIG. 3 depicts the apparatus operating in a hydrogenproduction mode. Since the purity of hydrogen gas produced exceeds 99.99vol. % (on dry basis), and it does not contain any potentially harmfulcontaminants such as carbon monoxide, hydrogen sulfide, ammonia, and thelike; hydrogen can be directly fed to any type of fuel cell, includingPEM fuel cell, to produce electricity.

The advantages of the present invention over known methods forgenerating or producing hydrogen from water, include, but are notlimited to, the elimination of a need for a preliminary preparation ofreacting solutions and the direct production of hydrogen from water; thevariety of sources of water can include tap, reclaimed, industrial gradewater and, even, seawater; inexpensive and readily available reagentsand materials are used; hydrogen gas release occurs immediately uponadding water to the chemical composition and does not requirepre-heating, mechanical activation or other ways of initiating thereaction.

The specific energy and power density characteristics of the system aresuperior to state-of-the-art systems due to the use of the combinationof two high-energy content components (i.e., components A and B) of thedisclosed chemical composition. The release of hydrogen gas startsimmediately upon the addition of water without any induction orwarming-up period that are required by state-of-the-art systems.

The preferred temperature range of the hydrogen releasing reaction(50-80° C.) is compatible with that of a power-generating system, e.g.,a polymer electrolyte membrane (PEM) fuel cell. The reagents and thereaction products used in the method can be safely handled during theoperation, and they are safe to humans, animals and environment.

The reaction products are easily disposable and could be recycled intooriginal reagents in a specialized facility. For example, metallicaluminum could be easily regenerated from the reaction products byconventional electrolytic and carbothermic processes.

Five possible uses of the present invention include, but are not limitedto, the following applications. The present invention can be used in theproduction of high purity hydrogen gas (>99.9 vol. %, not accounting forwater vapor) with no potentially harmful impurities such as CO, H₂S,HCl, unsaturated and aromatic hydrocarbons, and the like.

The present invention can supply hydrogen for electric power generationvia use of a fuel cell, preferably, a polymer electrolyte membrane (PEM)fuel cell, or other means of power production including turbines,internal combustion engines, diesel engines and the like.

The present invention provides a combined heat and power supply forresidential and industrial applications can be provided when using themethod of the present invention.

The present invention can be used in high-power density portable andminiature power systems for electronics and uninterrupted power supply(UPS) units.

The present invention can make hydrogen available for space and militaryapplications, including soldier power supply, unmanned aerial vehicles,air-independent propulsion for submarines, and the like.

While the invention has been described, disclosed, illustrated and shownin various terms of certain embodiments or modifications which it haspresumed in practice, the scope of the invention is not intended to be,nor should it be deemed to be, limited thereby and such othermodifications or embodiments as may be suggested by the teachings hereinare particularly reserved especially as they fall within the breadth andscope of the claims here appended.

1. A method for producing hydrogen from water comprising the steps of: a) selecting a vessel without water consisting of a first holding area for at least one metallic ingredient that can release hydrogen when reacting with water and a second holding area for at least one inorganic hydride that can release hydrogen when reacting with water; b) placing the metallic ingredient in the first holding area and the inorganic hydride in the second holding area within the vessel without water; c) keeping the metallic ingredient and inorganic hydride separate until the reaction with water is desired for the production of hydrogen; d) adding to the metallic ingredient at least one transition metal compound that can catalyze the reaction of the metallic ingredient and the inorganic hydride wherein the addition of the transition metal compound is prior to adding water; e) adding water to the vessel to cover the first holding area with the metallic ingredient-transition metal combination and the second holding area with the inorganic hydride; and f) collecting hydrogen released from the decomposition of water in a synergistic aqueous reaction of metallic ingredient and inorganic hydride at ambient conditions of temperature and pressure.
 2. The method of claim 1, wherein the metallic ingredient is selected from elements of groups IIA-IVA and VIII and alloys thereof.
 3. The method of claim 2, wherein the metallic ingredient is selected from the group consisting of aluminum (Al), magnesium (Mg), silicon (Si), iron, aluminum alloys, magnesium alloys, iron alloys and silicon alloys.
 4. The method of claim 2, wherein the metallic ingredient is aluminum.
 5. The method of claim 1, wherein the inorganic hydride is selected from a family of inorganic complex metal hydrides.
 6. The method of claim 5, wherein the inorganic hydride is selected from a group consisting of sodium borohydride, lithium borohydride, potassium borohydride, lithium aluminum hydride, sodium aluminum hydride.
 7. The method of claim 6, wherein the inorganic hydride is sodium borohydride.
 8. The method of claim 1, further comprising the steps of: adding an alkali metal-based compound to the inorganic hydride to stabilize the inorganic hydride prior to adding water to the vessel; and adding a transition metal compound from groups VIII and IB to the metallic ingredient prior to adding water to the vessel to catalyze the synergistic aqueous reaction resulting in hydrogen release.
 9. The method of claim 8, wherein the alkali metal-based compound is at least one of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), sodium carbonate (Na₂CO₃), and potassium carbonate (K₂CO₃).
 10. The method of claim 9, wherein the alkali metal-based compound is sodium hydroxide (NaOH).
 11. The method of claim 8, wherein the transition metal and its compound is cobalt, cobalt chloride (CoCl₂), cobalt bromide (CoBr₂), cobalt iodide (CoI₂), cobalt nitrate (Co(NO₃)₂, iron, iron (II) chloride (FeCl₂), iron (III) chloride (FeCl₃), ruthenium, ruthenium (III) chloride (RuCl₃), copper, copper sulfate (CuSO₄), platinum, chloroplatinic acid (H₂PtCl₆), nickel, nickel nitrate (Ni(NO₃)₂ and nickel chloride (NiCl₂).
 12. The method of claim 11, wherein the transition metal compounds are cobalt chloride (CoCl₂) and iron chloride (FeCl₂). 